Cyanoalkylamino substituted triazines having plant growth regulating action



United States Patent "ice 3,505,325 CYANOALKYLAMINO SUBSTITUTEDTRIAZINES HAVING PLANT GROWTH REGULATIN G ACTION Werner Schwarze,Frankfurt am Main, Germany, assignor to Deutsche GoldundSilber-Scheideanstalt vormals' Roessler, Frankfurt am Main, Germany NoDrawing. 'Continuation-in-part of application Ser. No. 652,036, July 10,1967. This application Nov. 20, 1967, Ser. No. 684,514 Claims priority,application Germany, July 16, 1966, D 50,605; Nov. 22, 1966, D 51,608Int. Cl. C07d 55/20; A01n 9/22 U.S. Cl. 260-249.8 11 Claims ABSTRACT OFTHE DISCLOSURE Compounds of the formula wherein X is a halogen atom,preferably, chlorine, lower alkoxy, lower alkyl mercapto,

each of R and R taken individually is hydrogen or lower alkyl or alkenyl(straight or branched chained) or lower alkyl or alkenyl substitutedwith OH, OR, SR or CN, R being lower alkyl, each of R and R takenindividually is alkyl or alkenyl or aralkyl groups of 1 to 8 carbonatoms and taken together form a 5 to 7 membered ring, in addition one ofR and R can be hydrogen, having herbicidal and plant growth regulatingproperties, compositions containing the same and method of regulatinggrowth of plants therewith.

RELATED APPLICATION This application is a continuation-in-part ofapplication Ser. No. 652,036, filed July 10, 1967, now abandoned.

BACKGROUND OF THE INVENTION The invention relates to novelcyanoalkylamino substituted-s-triazines having plant growth regulatingand, especially, herbicidal properties.

Herbicides have become known which contain an s-triazine ring and in the2 position carry an azido or alkyl mercapto group or halogen and in 4position carry a cyano-alkylamino group as active ingredient (BelgianPatents 656,233 and 644,355). However, in these compounds the cyanogroup is directly attached to a primary carbon atom and compounds ofthis type do not reach the activity of the best products availablecommercially.

A number of herbicidal substituted bisalkylamino triazines have alsobecome known. Some have, in practice, been found to be excellentherbicides, such as, for example, 2,4-bis-ethylamino6-chloro-triazines,2-ethy1amino-4- isopropylamino-6chlorotriazine,2-methyla-mino-4-isopropylamino6-methylmercapto-triazine and2,4-bis-isoproplyamino 6 methylmercapto-triazine.-These compounds allcontain 2 alkyl amino groups. 2-amino-4-a1kylaminotriazines with strongherbicidal activity have not become known.

3,505,325 Patented Apr. 7, 1970 SUMMARY OF THE INVENTION The inventionconcerns novel cyanoalkylamino substituted triazines of the formlawherein X is a halogen atom, prefarably, chlorine, lower alkoxy, loweralkyl mercapto,

each of R and R taken individually is hydrogen or lower alkyl or alkenyl(straight or branched chained) or lower alkyl or alkenyl substitutedwith OH, OR, SR or -CN, R being lower alkyl, each of R and R takenindividually is alkyl or alkenyl or aralkyl groups of 1 to 8 carbonatoms and taken together form a 5 to 7 membered ring, in addition one ofR and R can be hydrogen, having herbicidal and plant growth regulatingproperties, growth regulating and herbicidal compositions containingsuch novel compounds as active ingredient, as well as a method ofregulating or controlling the growth of plants therewith.

DETAILED DESCRIPTION OF THE INVENTION IN- CLUDING PREFERRED EMBODIMENTSTHEREOF According to the invention it was found thatcyanoalkylamino-s-triazines as described above in which the cyano groupis directly connected to a secondary or preferably a tertiary carbonatom which is also directly attached to the amino group on the triazinering are marked by their especially high and selectipe herbicidalactivity and are rapidly decombosed in the soil. In the description theterm lower as in lower alkyl, lower alkoxy and lower alkenyl is intendedto signify groups with 1 to 4 carbon atoms.

The novel compounds can be prepared by conventional methods known tothose skilled in the art. For instance, 1 mol of cyanuric chloride canbe reacted with 1 mol of an amino nitrile of the formula ON H503/ NHzThese u-arnino nitriles are produced by conventional methods, such as,for instance, by first reacting ketones or aldehydes with hydrocyanicacid in the presence of an alkaline catalyst to form the correspondingcyano hydrine and reacting the latter with ammonia to produce thedesired amino nitrile. The synthesis also can be carried out in oneprocess step by reacting the ketone or aldehyde, hydrocyanic acid andammonia with or without a diluent. A mixture of ammonium chloride andalkali metal cyanide can be used instead of free hydrocyanic acid. Inthe latter instance the reaction is carried out in the presence ofwater. The a-amino nitriles are water white liquids which can bedistilled under vacuum. They are relatively unstable but can be kept ina refrigerator (0 C.) for several days without decomposition.

The alkyl mercapto derivatives can, for example, be produced by reactionof the corresponding chloro substituted triazines With an alkylmercaptan in the presence of an acid binding agent. It also is possibleto start from 2- alkylmercapto 4,6 dichlorotriazines which aresequentially reacted with an amino nitrile in the presence of an acidbinding agent and in the presence of an amine again in the presence ofan acid binding agent. It furthermore is possible first to introduce anamino group into the triazine and then the alkyl mercapto group andfinally again an amino group (starting, for example, from cyanuricchloride).

The alkoxy derivatives, for instance, can be produced in high yields byreacting the corresponding chloro substituted triazines with sodium orpotassium alcoholates in an alcohol at raised temperatures and, ifdesired, raised pressures. The cyanuric chloride also can first beconverted to the 2-alkoxy-2,4-dichlorotriazine by conventional methods,for example, by reaction of cyanuric chloride with alcohol in collidineand then reacting the intermediate with the amino nitrile and the aminein any desired sequence. It also is possible analogously to start with a2 alkylamino 2,4 chlorotriazine and reacting this with an alcohol andwith an amino nitrile in any desired sequence.

Azido triazines of the type concerned can be produced by reaction ofchlorotriazine with an alkali metal or ammonium azide in dimethylformarnide or dimethyl sulfoxide or even better by reacting such azideswith a quaternary methyl ammonium compound in water.

Another method for the production of the compounds according to theinvention involves starting from a 2 amino-, alkyl aminoor cyanalkylamino-2,4-dichlorotriazine and such compound is converted to the2-amino-, alkyl aminoor cyanaklyl amino-4-azido-6-chlorotriazin byreaction with an aqueous alkali metal azide solution in the presence ofappropriate solvents such as acetone or tetrahydrofurane. Theintermediate azido compound is then converted to the desired productwith an amino nitrile, ammonia or an amine.

The compounds according to the invention are marked by their superiorherbicidal properties and can be used as pre-emergence or post-emergenceherbicides. They are already able to influence the growth of plants Whenapplied in low concentrations. Depending upon the nature of substituentsR R they can be used for the destruction or selective suppression ofweeds among cultured plants, as well as for the total destruction andprevention of undesired plant growth.

The novel compounds according to the invention can also be used, forexample, for defoliation, reduction of set of fruit, delay in flowering.They can be used individually or in admixture with each other or alsowith insecticides, fungicides and fertilizers.

The following is a tabulation of compounds according to the inventionhaving the structural formula given in the summary of the invention withthe substituent X and R R indicated.

Melting R 2 R 3 R 1 Point, 0. Appearance H CH CH3 191-192 Whitecrystals. H CH3 C2115 178-179 DO. 0 H C Ha C H5 201-201 D0. CH3 CH3C2119 151-152 DO. CH3 CH3 0411 -1 141-142 D0 CH3 C 2 5 2H5 177-178 D0.

CH CH2-CH2 183-184 Do.

\ /C\ /CH2 CHr-CH C] H C2115 CH3 CH3 161-162 D0. Cl H CzHs CH3 CzHs136-137 D0.

Cl H C2115 CH3 CH3 141 Do.

Cl H C2115 CHE-CH2 134-136 Do.

CH2-CH2 CzHs CzHs C2H5 -15 D0. C H -i CH3 CH3 188-189 D0. CsH7-1 CH3C2115 156 D0. CaHv-i CH3 CaH'r-Il 148-149 D0. CaHv-i CH3 CiHq-i 121 D0.04119-11 CH2 CH3 149-150 D0. 0 HzCHzC H2O CH3 CH CH 124-125 Do.CHzCHzSCHs CH CH3 127-129 Do,

CHBCN CH CH 166-167 D0. CH2CH2OH CH3 CH3 148-149 Do. CHaCH=CHg CH3 CH136-138 Do. CH3 CH3 CH3 124-125 D0. C3H7-1 CH3 CH3 141-143 DD. CH3 CzHsC2Hs 118-120 DO. 0 117-1 C2115 C2115 103-105 D0. CH2OBH5 CH3 CH3 126-128D0. CH OE-:01 CH CH 83-85 Do. CHzCHzOH CH: CH3 99-100 D0.

Melting X R 1 R 2 R 3 R 4 Point, 0. Appearance H H CH3 CzH 135 White5122118. H CH3 CH3 02H 121-122 DCL H CzHa CH3 (12H DO. 1222 5 82%: i 8%3gzz H Y llow O a 1- a a 91-92 White er stals: H CHzCHzCN CH3 02H 110-112D0. y H H CH CaH i 212-214 D0. H CH3 CH3 C H1-1 122-124 Do. H C 3H7-1 CH3 C 3H7-1 129-131 D 0 H C2115 CH3 C Hu-l 93-94 DO.

H H CH2C H2 191-193 D0.

CHzC H:

SCH: H CH3 CHz-CH: 139-141 D0.

CHzCHg SCHa H C3H7-i CHz-CH: 127-128 1 DO.

C CH:

CHa-CH:

H C2115 CH3 CH3 126-127 D0. H C2115 CH3 C2H5 83-84 D0. H CzHs CH3 CH1;96-97 D0. H CzHs C H3 CZ E 71-72 D0. H H C H3 CH 193-(Z) D0, H. C2115CH3 CH3 102-105 D0. H (CHg) CH3 CH3 CH3 92-93 DO. H H 0H: CH5 128-130D0. H C H7-1 CH3 C 115 69-70 DO. H (CHz)3OCH3 CH3 021115 78-79 D0. H HCH3 CaH7-i 164-165 D0. H (CH3) so CH3 CH C3H -1 109-111 DO. H CH3 CH3C4H9-i 130 D0. H CH3 CH3 Cilln-n 97-98 DO. H CH CH3 C5H11-1 105 D0. HCgHs CH3 csHn-i 120 D0.

CHz-CHz H H 0 CH: 201 D0.

CHr-CH:

H C 11 CH3 CzHa 85-87 D0. 11 C H -1 CH3 CzHs 100-103 D0. H CH3 H 198-200D0. H C3H1-1 CH3 H 200-201 D0. H CzHs 1-C3H7 H 136-137 D0. H C3H7-11-CaH7 H 140-142 Do. H (J E n-CaH7 H 185 D0. H -CHgCHz-C H2-O CH3 CH3 H131-132 D0. 11 C H -1 C H; H 94-95 D0. H -CH2'CH:CH2-O CH3 CH3 H 87-88D0. H (3,5 0 Ha H 79-81 Do. H 11 C H3 H 94-95 D0. H CaH'i-i CH3 H 86-87D0. H CzHs C 3 H 91-92 DO. H C Hr-CHrCHgO CH3 CH3 H 104-105 D0. H CH3CH3 H 175-176 D0. H C 11 02115 K 108-109 Do. H CH3 CaH7-1 K 148-149 D0.H 13 05H; H 171-173 Do.

It was very surprising and unexpected that the triazines according tothe invention which contain a tertiary or secondary C atom attacheddirectly to an amino group and directly to a cyano group would beextremely strong herbicides as corresponding compounds containing acarboxarnide, a carboxy or a carboalkoxy group instead of the cyano-group,-such as, for instance, 2-ch1oro-4- ethylamino 6 (1methyl-l-carbamoylethyl)-amino-striazine and 2 chloro4-ethylarnino-6-(l-methyl-l-carboxyethyD-amino-s-triazine have nophytotoxic action whatsoever.

The excellent herbicidal 'action of the compounds according to theinvention therefore depends upon the presence of the cyano group whichmust be bound directly to a tertiary or a secondary C atom.Cyanoalkylamino triazines which carry the group -NH(CH -CN are much lessactive.

The chlorotriazines which have been introduced in practice have a longpersistence in soil, which often is undesired. In comparison therewiththe triazines according to the invention are decomposed in soil in arelatively short period of time.

The ehlorotriazines according to the invention are very selective incorn cultures. In this connection they, for

H CH3 CH3 CH3 CH3 CH3 C2H5 CH: C 3 CaH' -l CH3 CH H CH3 C2H5 CH3 CH3CzHs CzHs CH3 CzHs CH5 CH3 CaHv-n H CH3 CH3 The selectivity of thecompounds according to the inventron, however, is not restricted tocorn. They also have herbicidal selectivity in cultures other than corn,depending on their constitution as illustrated by way of example by thefollowing:

SELECTIVE IN WHEAT X R R R3 4 C3 7-i CH3 03H7-l. C 3 C2H5 CzHs CH3 C2H5CzHs CH3 CH C H7-l SELECTIVE IN RICE C1 H CH3 CH O3H7-i /CH2CE2 C1 H CH3/C\ /CH2 CH CH2 Cl H CH3CH=CH2 CH3 CH3 SCH: H C2H5 CH3 CzHs SELECTIVE INCOTTON C3H7-i CH3 CH3 CH CaHs C2H5 C2H5 C 3 CH3 C2H5 CH3 C The compoundsaccording to the invention, depending upon their substituents, displayan outstanding preemergence and/or post-emergence activity. In mostinstances they are crystalline and have good solubility in many organicsolvents. This differentiates them from the known bis-alkylaminochlorotriazines which are very difficultly soluble in most usual solvents. Thenovel compounds therefore are well adapted for spraying over fields fromaeroplanes in the form of solutions in solvents.

The following, for instance, come into consideration as solvents for thecompounds according to the invention: alcohols, ketones, hydrocarbons,halogenated hydrocar-bons, for instance, chloronaphthalene, mineraloils, such as, diesel oil, vegetable oils or mixtures thereof.

The novel triazine compounds can also be applied to solid carriers. Assuch, all known agricultural carriers come into consideration, forexample, alumina, kaolin, kieselguhr, bentonite, talc, finely groundcalcium carbonate, charcoal, wood flour and the like. The activecompounds can be admixed in dry form with the carriers. It, however,also is possible to spray solutions or emulsions on or mix them with thecarriers and drying the resulting mixtures. In order to obtain betteradhesion of the active substances on the carriers, known adhesives, suchas, glue, casein, alginic acid salts and the like may be employed.

It also is possible, for example, to mix the triazine compounds, ifdesired, together with carriers, with suspending agents and stabilizersto produce a paste or powder which then can be mixed with water to forma suspension.

Known anionic, cationic or non-ionic substances can be employed aswetting agents, emulsifiers and stabilizers, such as, for instance,turkey red oil, fatty acid salts, alkyl aryl sulfonates, secondary alkylsulfates, resin acid salts, polyoxyethylene ethers of fatty alcohols,fatty acids or fatty amines, quarternary ammonium compounds, ligninsulfonic acid, saponin, gelatine, casein, either alone or in admixture.

The following examples will illustrate representative preparations ofcom ounds according to the invention, active compositions containing thesame and their ap lication.

Example 1.2-chloro-4-amino-6-( 1-cyano-1-methylethyl) -amino triazine184.5 g. of cyanuric chloride were suspended in 750 ml. of acetone andthe suspension cooled to C., then 85.7 g. of a-amino-isobutyronitrile(1.02 mol) were added gradually while maintaining a temperature notabove C. Thereafter a solution of 40 g. NaOH in 100 ml. of H 0 was addedgradually, care being taken that the pH did not rise above 8. Then 200g. of a 17;% ammonia solution were added gradually without externalcooling. The temperature gradually rose to 30-35 C. The mixture wasstirred until it reacted neutrally. The acetone was then drawn off undervacuum and water added to the residue. The resulting thick crystal pastewas filtered off, washed with water and dried under vacuum at 50 C.Yield: 174.4 g. (82% of theory). Thin layer chromatogram: 98%.

Analysis.Calculated for C H N CI, Mol. wt. 212.5 (percent): C, 39.5; H,4.3; N, 39.5; CI, 16.7. Found (percent): C, 39.7; H, 4.4; N, 39.5; CI,16.6.

Example 2.2-chloro-4-ethylamino-6-( 1cyano- 1- methyl-propyl)-amino-triazine 184.5 g. of cyanuric chloride were suspended in 1 literof tetrahydrofurane and the suspension cooled to 0 C. While maintainingthis temperatures and stirring, 100 g. of a-aminoisovaleronitrile werefirst added gradually and then g. of 50% aqueous NaOH added gradually.The mixture quickly became neutral. The cooling was suspended and g. ofa 50% aqueous ethylamine solution was added, permitting the temperatureto rise, and then again 80 g. of 50% aqueous NaOH gradually addedthereto. The maximum temperature reached was 45 C. After processinganalogously to Example 1, 240.5 g. of a snow white product of a meltingpoint of 139141 C. were obtained.

Analysis.Calculated for C H N Cl, Mol. wt. 254 (percent): C, 47.2; H,5.9; N, 33; Cl, 13.9. Found (percent): C, 47.2; H, 6; N, 33.1; CI, 14.1.

2 ethylamino-4-(1cyano-ethyl)-amino-6-chl0ro-s-triazine of a meltingpoint of 174175 C. was produced analogously from cyanuric chloride,a-alanine nitrile and ethyl amine.

Example 3 .2-rneth0xy-4-ethylamin0-6-( l-cyano- 1- methyl-ethyl)-aminotriazine 240.5 g. of2-chloro-4-ethylamino-6-(l-cyano-l-methylethyl)-aminotriazine were addedto 1 liter of methanol containing 54 g. of sodium methylate at 3035 C.The reaction was weakly exothermic. The reaction mixture was kept at3035 C. for 4 hours and then at 60 C. for 1 hour. The solution thenreacted neutral. The methanol was evaporated off under vacuum and theresidue taken up in water and the crystals formed filtered off, washedwith water and dried. Yield: 227 g. Melting point: 138 C.

Analysis.Calculated for C H N O, Mol. wt. 236 (percent): C, 50.8; H,6.8; N, 35.6. Found (percent): C, 50.7; H, 6.9; N, 35.7.

2-ethylamino-4-( l-cyano -ethyl-6-n1ethoxy-s-triazine of a melting pointof 9495 C. was prepared analogously from the corresponding 6-chl0rocompound.

Example 4.2 methylmercapto-4-[3-cyanoethylamino-6-l-cyanol-methyl-propyl) -amino-triazine 279.5 g. of2-ch1oro-4-,8-cyanoethylamino-6-( l-cyanol-methyl-propyl)-amino-triazinewere added to a solution of 70 g. of sodium methylmercaptide in 1 literof methanol and the mixture heated for 12 hours at 40-45 C. The reactionmixture was boiled down under vacuum and the residue taken up in water.After filtering off, washing and drying, the resulting crystals, 284 g.of a white crystalline powder of a melting point of 110112 C. wereobtained.

Analysis.Calculated for C H N s, M01. wt. 291 (percent): C, 49.5; H,5.8; N, 33.7; CI, 11.0. Found (percent): C, 49.7; H, 5.8; N, 33.6; C1,11.0.

2 ethylamino-4- l-cyano-ethyl -6-1nethyl-mercapto-striazine of a meltingpoint of 7981 C. was prepared analogously from the corresponding6-chloro compound.

hexyl)-amino-triazine were added to 1 liter of isopropanol and 70 g. ofsodium azide and ml. of an aqueous solution of 20 g. of trimethylamineadded thereto. The temperature rose slightly. The mixture was thenheated for 4 hours at 40-45 C. The solvent was then evaporated off undervacuum and the residue taken up in water. After filtering off theresulting crystals, washing and drying, 267.5 g. of white crystals of amelting point of 97-98 C. were obtained.

Analysis.Calculated for C N N M01. wt. 289 (percent): C, 49.8 H, 6.6; N,43.6. Found (percent): C, 49.7; H, 6.8; N, 43.3.

2 ethylamino 4(l-cyano-ethyl)-amino-6-azido-s-triazine of a meltingpoint of 91-92 C. was prepared analogously from the corresponding6-chloro compound.

Example 6.--2-isopropylamino-4-ethylamino-6-(l-cyanol-methyl-ethyl)-amino-triazine An aqueous solution of 120 g. of isopropylamine in 600ml. of H was placed in a 2 liter autoclave and 240.5 g. of2-chloro-4-ethylamino-6-(l-cyano-l-methylethyD-amino-triazine addedthereto. After closing the autoclave it was heated to 100-110 C. for 4hours. After processing the reaction mixture in a manner analogous tothat of the preceding examples, 253 grams of a white crystalline productof a melting point of 91 to 92 C. were obtained:

Analysis.-Calculated for C12H21N7, Mol. wt. 263 (percent): C, 52.8; H,7.2; N, 28.8; S, 10.6.

Example 7.-2-propylmercapto-4-ethylamino-6-( lcyanol-methylpropyl)-amino-triazine 224 g. of 2-propylmercapto-4,6-dichlorotriazine weredissolved in 500 ml. of acetone and 98 g. of u-amino-isovaleronitrileadded slowly while cooling to to C. and then a solution of 40 g. of NaOHin 100 ml. of H 0. The pH of the solution was between 7 and 8. Then 90g. of a 50% ethylamine solution and 100 g. of a 40% NaOH in H O wereadded. The mixture was heated under a reflux condenser to 60 C. whilestirring for 3 hours. The solvent was distilled OE and the residue takenup in water. A thick crystal paste formed which was further washed anddried. Yield 282.5 g. corresponding to 96.3% of theory, melting point7l-72 C.

Analysis.--Calculated for C H N S, M01. Wt. 294 (percent): C, 53.1; H,7.5; N, 28.6; S, 10.9. Found (percent}: 52.8; H, 7.2; N, 28.8; S, 10.6.

Example 8.2-ethylmercapto-4-ethylamino-6-(1-cyanol-methylethyl)-amino-triazine 21 g. of2-ethylmercapt0-4,6-dichlorotria2ine were introduced into 100 ml. ofacetone and 8.3 g. of a-aminoisobutyronitrile slowly added to suchsolution. Subsequently a solution of 4 g. of NaOH in 15 ml. of H 0 wereadded slowly. The temperature was C. Then 9.1 g. of a 50% solution ofethylamine were added at 40 C. and subsequently 4 g. of NaOH in 15 ml.of H 0.

The solution was then heated under reflux for 4 hours. It reactedneutral at the end. The acetone was removed under vacuum and the residuetaken up in water. Crystallization was completed in a short period oftime. 24 g. of white crystals of a melting point of 126l27 C. or a 91.2%yield were obtained.

Example 9.2-chloro-4-methylamino-6-(l-cyanocyclohexyl)amino-triazineExample 10 136.5 g. of acetone were placed in a three liter round flaskand cooled to +5 C., then 5 ml. of triethylamine were added andsubsequently 650 g. of liquid hydrogen cyanide were gradually added froma cooled supply. The reaction was exothermic. After completion of thereaction the pH of the solution was adjusted to 2 with 50% phosphoricacid.

An autoclave was filled with 1800 ml. of liquid ammonia and afterclosing the acetone cyanhydrin was pumped in. The temperature rose to 40C. and the mixture was subsequently heated to 50 C. for 3 hours. Aftercooling down the contents of the autoclave were removed. The crudeproduct was a light yellow liquid. It was rendered water free bytreating it three times with solid KOH and then fractionally distilledunder vacuum in a 1 meter column with a dephlegmator. At 48-50 C. undera pressure of 13 mm. Hg colorless u-aminoisobutyronitrile distilled overin a quantity of 1756 g. (88% of theory).

The following a-arninonitriles R2 RJ--NHz were analogously prepared bythis method:

64.2 g. (1.2 mol) of ammonium chloride were dissolved in 200 ml. ofwater and then 78 g. of potassium cyanide slowly added thereto whilestirring and cooling. Thereafter, 86 g. of methyl isopropyl ketone (1mol) were slowly added to the mixture at 15 to 20 C. and the mixturestirred for 2 hours at this temperature. Subsequently ammonia gas waspassed through the mixture While stirring for 2 hours, the temperaturebeing slowly raised to 50 C. After cooling down the mixture was placedin a separatory funnel and shaken out three times with ether. The etherextracts were united and dried with Na SO and the solvent distilled offunder vacuum. The residue was distilled over a small column undervacuum. The desired l-methyl-1-cyano-2-rnethyl-n-butylamine distilledover at 6061 C. at a pressure of 12 mm. Hg as a water white liquid. Theyield was 86 g. or 76.7% of theory.

The remaining novel cyanoalkylamino triazines according to the inventionshown in the table preceding the examples, as well as in the followingexamples, were prepared by methods analogous to those described in theabove examples employing the appropriate amine, ammonia, azide,alcoholate, alkyl mercaptide, cyanoalkylamine and halo-s-triazine asstarting material. In the following, parts signify parts by weight.

Example 12 10 parts of 2-methylamino-4-(1-cyano-1-methyl-ethyl)-amino-6-chloro-triazine, 89 parts'of bentonite, 1 part of finely dividedpyrogenic silica were ground together in a ball mill to a fine dust. Themixture can be applied as a dust.

Example 13 A mixture of 10 parts of 2-ethylamino-4-(1-cyano-1-methyl-n-propyl)-amin-6-methoxy-triazine and 90 parts of kieselguhr wasground together to produce a dust of extreme fineness suitable forapplication as a dust.

Example 14 50 parts of 2-ethylamino-4-(1-cyano-1-methylethyl)-amino-6-azido-triazine were dissolved in 450 parts of kerosene. Thesolution can be used directly for spray applications.

- Example 17 parts of 2-methylamino-4-(1-cyano-ethyl)-amino-6-chloro-s-triazine, 89 parts of bentonite and 1 part of finely dividedsilica were ground in a ball mill to a dust of extremefinen'ess. Themixture is suitable for application as a dust.

Example 18 A mixture of 10 parts of2-ethylamino-4-(1-cyanopropyl)-amino-6-methoxy-s-triazine and 90 partsof kieselguhr was similarly ground in a ball mill to adjust of extremefineness to provide a mixture suitable for application as a dust.

Example 19 A mixture of 20 parts of 2-isopropyl-amino-4-(1-cyano-ethyD-amino-6-methyl-mercapto triazine, 70 parts of chlorobenzeneand 10 parts of an octyl phenyl polyglycol ether (Hostapal CV, producedfrom di-t-butyl pheol and 10-12 mol of ethylene oxide). This preparationupon mixture with water gives a stable dispersion.

Example 20 25 parts of 2-isopr0pyl-amino 4 (1-cyano-pr0pyl)-amino-6-chloro-s-triazine were dissolved in parts of cyclohexanone, 15parts of chlorobenzene and 10 parts of a substituted naphthalenedisulfonic acid, such as, Nekal BX. The mixture upon admixture withwater gives a stable emulsion.

Example 21 50 parts of Z-ethylamino 4 (1-cyano-ethyl)-amino-6-azido-s-triazine were dissolved in 450 parts of kerosene, The mixturecan be sprayed directly.

. Example 22 The following tests were carried out to investigate theherbicidal activity of compounds according to the invention:

(a) Pre-emergence soil treatment after seeding-Various seeds were sownin soil in plastic dishes in a greenhouse maintained at 21 C., wateredin the morning and in the afternoon, treated with a dispersion obtainedby pouring a solution of the herbicide in equal quantities of water.Thereafter the sprouting of the plants was observed with normal wateringand after 2 weeks it was determined whether and to what extent the plantgrowth had been suppressed.

(b) Post-emergence soil treatment.The seeds were sown and maintained ina greenhouse in the same manner as under (a) except that the applicationof the herbicide to the soil was efiected after sprouting. After 2 weeksit was determined if and to what extent the plant growth had beenreduced.

(c) Leaf treatment.-The procedure as described under (b) was followedexcept that the herbicide was applied to the plant leaves rather thanthe soil.

The results of the tests are given in the following tables. The growthwas evaluated according to a scale ranging from 0 to 9 in which 0signifies normal growth and 9 total destruction of the plant.

The active substance concentration in tests under (a) corresponded to 20kg./hectare and in tests under (b) and (c) 10 kg./hectare and 1kg./hectare using the following compounds:

(I) 2-amino-4-(l-methyl-l-cyano-ethyl)-amino-6- chloro-triazine (II)2-methylamino-4-( l-methyl-l-cyano-ethyl) -amino- 6-chloro-triazine(III) 2-ethylamino-4- l-methyl-l-cyano-ethyl) -amino- 6-chloro-triazine(IV) 2-ethylamino-4-( 1-methyl-1-cyano-n-propyl) amino-6-chloro-triazine(V) 2-methylamino-4-( l-methyl-l-cyano-ethyl) -amino- 6-azido-triazine(VI) 2-ethylamino-4- l-methyl- 1 -cyano-ethyl -amino- 6-azido-triazine(VII) 2-ethylamino-4-(1-methyl-1-cyano-ethyl)-amino-6-methylmercapto-triazine (VIII) 2,4-bis-ethylamino-6-chloro-triazine(IX) 2-ethylamino-4-isopropylamino-6-chloro-triazine (X)2-ethylamino-4-t-butylamino-6-methyl-mercapto- 6O triazine TABLE Test(a) y Sugar Substance used Corn Oats grass Peas Linseed Mustard beet 4 98 6 9 9 9 0 8 8 6 9 9 9 0 8 8 5 5 9 9 0 8 8 5 9 9 9 4 8 8 4 9 9 9 4 7 74 9 9 9 6 9 9 7 9 9 9 Comparison VIII 0 6 7 5 9 9 9 Comparison IX 0 7 85 9 9 9 Comparison X 3 7 8 4 9 9 9 TABLE Test Kg./ Rye Sugar Substanceused hectare Corn Oats grass Peas Linseed Mustard beet 10 4 9 8 7 9 9 91 O 8 4 6 9 9 8 10 0 8 3 9 9 9 1 0 8 4 2 9 9 9 1 9 9 5 9 9 9 1 0 8 7 5 99 9 10 0 8 8 5 9 9 9 1 0 7 6 3 9 9 9 10 2 8 8 4 9 9 9 1 0 7 4 0 5 9 9 102 8 8 3 9 9 9 1 1 8 7 1 9 9 9 10 6 9 9 6 9 9 9 1 1 9 s s 9 9 0Comparison VIII 10 3 6 4 5 6 9 8 1 0 3 2 4 3 7 6 Comparison IX 10 1 6 65 9 9 9 1 0 5 5 5 8 9 9 Comparison X 10 3 8 9 6 9 9 9 1 '2 7 8 6 9 9 9Test c) 10 2 8 9 1 9 9 9 1 0 6 4 0 6 6 8 10 0 8 8 3 9 9 9 1 0 5 4 0 7 87 10 0 7 8 3 9 9 9 1 O 4 4 0 7 9 8 10 0 7 8 1 8 9 9 1 0 3 3 0 8 9 8 10 47 9 3 9 9 9 1 0 1 1 1 8 9 9 10 4 7 9 2 8 9 9 1 0 4 4 0 7 9 3 10 6 8 9 39 9 9 1 1 4 2 0 7 7 9 Comparison VIII 10 0 4 6 1 6 8 7 1 0 2 4 0 4 6 7Comparison IX 10 1 5 7 3 8 9 7 1 0 3 5 2 5 8 6 Comparison X 10 3 7 8 3 99 9 1 0 4 4 0 9 9 8 Example 23 Oats, mustard and linseed were sown inseed pans filled with earth. After the plants had reached a height of 8cm. they were treated with an 0.5% emulsion of 2- ethylamino 4-(1-cyano-1methyl ethyl) aminofl6- methoxy-triazine. After 18 days allplants were destroyed.

Example 24 The following further tests were carried out to investigatethe herbicidal efficiencies of the compounds according to the invention:

(a) Pre-emergence soil treatment after seeding.-Seeds of test plantswere sown in narrow strips in plastic flats (38 X 13 x 6 cm.) filledwith John Innes potting compost. The seeding, watering and spraying withthe herbicidal agent occurred on the same day. Various concentrations ofthe active substances were used and the phytotoxicity ascertained byvisual inspection after about 14 days. The evaluation of the tests wasupon the basis for a scale ranging from O to 9 in which 0 signifiesnormal growth and 9 total destruction of the plant. The phytotoxicityfor each type of plant was converted to percent and plotted in plasticplates 9 cm. in diameter. After sprouting the plants were sprayed withthe herbicidal agent at various concentrations. After 10 days ofphytotoxicity and PD were determined as under (a).

When agropyron repens was used as the test plant, the sprouts were cutoff at the surface of the soil and the further growthafter 3 furtherweeks determined.

The PD values for the various plant varieties tested are given in thefollowing tables, I (according to a) and II (according to b).

The compounds according to the invention tested were of the formula R1,R R and X have the significance indicated in the tables for thecompounds tested.

In comparative tests 7a, 12 and 18, the group indicated under R and Rreplaces the group against the concentration of the active substance andthe s PD determined therefrom, that is, the active substance A -NH- GNconcentratlon providmg a 50% reduction of the plant growth.

(b) Post-emergence treatment.The seeds were sown in the compoundsaccording to the invention.

TABLE I (Test a) Finger Fox X R1 R3 R4 Corn Wheat Barley Rice grass tail0,115- CHs- C7H5- 5 2.6 3.6 2.2 1.6 1.2

onan- OH3- CH3 1.2 0.21 0.22 (1) 0.1 0.1

H CH CH3- 5 0.84 0. 23 (1) 0.1 0.1

(CH2)1OCH1 CH3- CH5 5 0.20 0.29 (1) 0. 29 0.1

C1115 NHCQlIri (comparison) 6 0.82 1. 1 0. 6

TABLE I-Conlt:lnued Barnyard grass (echino- (Chenochloa Sugar KnotMaypodium crusgalli) Cotton beet Cabbage Plantain Chicory grass weedClover album) 1 Not tested.

TABLE II (Test b) Barnyard (echino- Iest; Bar- Finger chola Rye No. X RR R Com Wheat ley Rice grass Foxtail crusgalli) grass CzH5- CH3- CHa 0.76 0. 18 0. 1 0. 22 0. 68 0. 1 (1) 0. 12 c2H5 CH;- C2H5- 1. s 0. 62 0.52 0. 65 0. so 0. 37 (1) 0. 26 C2H5- CH3- CH3 0. 95 0. 0. 1 0. 0. 15 0.1 0. 14 OzH5- CH3 CH3 0. 7 0. 1 0. 1 0. 16 0. 1 0. 11 O. 1 C H(CH2)zCN(compar1son) 5 2. 7 1. 1 3. 6 5 1. 7 2. 9 H CHa- CHa 5 0. 48 0.27 0. 58 0. 90 0. 34 0. 58 H CHs- CH3 0. 19 0. 11 0. 1 0. 02 0. 1

15 ol- CH3 H 5 0.58 0. 41 5 4. s 0. 09 3.6

C1- (CH2)3O CH3 CH5 CH3 5 0. 34 0. 13 0. 58 0. 27 0. 1 0. 28 CH O-(CH2)3O CH3 CH5 CH3 0. 17 0. 07 0. 26 0. 06 0. 07 01 02115 NHCaH7=1(comparison) 5 0. 1 0. 3 0. 45 0. 1 0. 36

(Cheno- Test Agropyron Agropyron Plan- Knot podium o. repens repensregrowth Cotton Sugar beet Cabbage Carrots tain Chicory grass album)Linseed Mustard 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 12 0. 23 (l) 2. 3 0. 190. 11 0. 1 0. 14 0. 19 0. 18 0. 18 0. 1 0.10 0.1 0.1 0.1 0.1 0.]. 0.1 010.1 0. 11 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 1. 2 4. 2 0. 54 1. 43. 2 5 5 5 (1) 0. 1 0. 1 0.30 0. 12 O. 17 0. 18 0. 15 0. 1 0. 02 0. 020. 06 0. 05 0. 01 0. 27 0. 59 0. 06 0. 08 0. 62 0. 09 0. 08 0. 06 0. 060.17 0.1 0.1 0.1 0.1 0.1 0.15 0.1 0.1 0. 02 0. 02 0. 04 O. 04 0. 01 0.25 0. 08 0. 08 0. 0. 13 0. 17 0. 08

TAB LE 1 Example 25 [X=C1; B =H] Leaf Pre-e Tests were carried out toinvestlgate the herblcidal a treatgenc s il efiiciency of compoundsaccording to the invention in the R R3 treatment form of solutions orsuspensions in a mixture of equal 6 3 4 3 parts of water and acetonewhich in addition contained 1% of a normal commercial dispersing agentand 2% of glycerine. The following plant varieties were used in thetests: corn, wheat, rye grass, peas, linseed, mustard and sugar beet. 5

The application in one series was to the leaves of the plant varietiestested and in the other series to the soil as a pre-emergenceapplication.

In the leaf treatment the formulation of the compounds was sprayed onthe leaves of the plants with the aid of a spray at a dosage rate of 1kg./ hectare.

In the soil treatment the seeds of the plant varieties tested were sownin earth in plastic dishes and watered shortly before application of theformulation tested and also simultaneously with the leaf treatment sothat equal quantities of the active substance were used.

At the end of the test periods (7 days in the leaf treatment and 11 daysin the pre-emergence soil treatment) the results were determined byvisual inspection. The evaluation was upon the basis of a scale rangingfrom 0 to 9 in which 0 signifies normal growth and 9 total destruction.The average phytotoxicity with all seven plant varieties tested with anactive substance application rate of 1 kg'./ hectare. Table 1-5 concerncompounds according to the invention which are identified according totheir substit uents X and R R as in the tables in Example 19. Table 6concerns previously known s-triazine compounds which are also identifiedaccording to their substituents.

(CH2)3OCH3 CH3 (CH2)3OCH3 CH (CHflzOC CH3 (CH2)3OCH3 C 11 (CH2)3OC2H5 CHH CH3 0C2H5 CH NH CzHs H TABLE 1Continued TABLE 5a [X=Cl; R1=H] [X=OH R=H] Leaf Preemer- Leaf Pre-emertreatgence soil treat gence soil R2 R.1R4 ment treatment R2 R3 R4 ment treatment CH3 CH3 7.4 6.7 CE; 6.9 5.9 CHCH3 7.6 6.9 CH3 on; CH3 7.8 0.1 C2135 6. 9 5. 6 CH3 CH3 0 5 8 03111-11on; CQHB 7.7 5.7 -1 on; C2115 7.7 5.4 CH3 C3H1-i 7.4 4.9 03H? CH3 C3H1-i2.0 4.6 CH3 C3H7-i 7. 6 3. 6 8 5 8 t2 2'2 2 2 3 n H] CH2 CH 0.9 4.0

tLeaf Pre-emerii C g rea. ence so 2 5 R7 R3 R4 mer t; tigdtment(CHQQOGHS H CH3 L3 7.0 3.3 161111 3.: 3. 9 TABLE 5b CI i a: 0:0 119 lff: Leaf Pro-emer- CH3 a 3.7 treatgence soil 82115 7,3 0 R2 R3 R4 menttreatment 0 11 3111111 513 iii 02H. 3 3 5.7 02115 6,3 L5 02H; CH3 CZHBCH; CH3 6,7 0, C2H5(X=NHC2H5) CH3 (72H; 6-4 1.3 C2H5 CE; 6.4 1.3 CH8 2-2gigtggga 1 712 at; TABLE (P-KNOWN COMPOUNDS 2 3 3 3 2 5 i (057780011,gut ggn-i substlmentmposltwn ag? 52x33; 0:115:13:1313;131:3311:1:33:33:H CH; 629 3:6 4 6 mm treatment C1 -NHC2H5 -NH(CH:):CN 2.4 2.0 rea aasaesa a; c 3 2 Z 2 5 s 7- ease aesaes t2 :2

-1 2 ea; sa es a .2

2 R7 R3 R4 ment treatment CL NHC (CHWCOOH 0 0 CH3 7 4 4 0 Cl... NHC2H5-NHC(CHa)zCONHz 0 0 CPIa 7: C1 '-NHC2H5 -NHC CH3)2COOCH3 0.2 0. 2 CH 7.74.3 0H3 7.6 0.2 CH3 7.1 2.3 Example 26 as 7: 2 5 CsHs 8.2 5.4 Thefollowing procedure was used to determine the Sig ability of thecompounds according to the invention to C H -i 7.4 3.4 decompose insoil:

3:2 21% Air dried loam was brought to a moisture content of CzHs 7.4 4.620%. The active substances tested were introduced into 3:; 2 kg.portions of such soil as a solution in 5 m1. of C5 u-H 6.9 0.9 acetoneto provide a concentration of active substance gfig if, if;corresponding to 0.3 kg./hectare. The treated soil was C2 5 H C5Hu-1 6.71.3 stored in covered plastic containers for varying lengths 5 3 8%; 8%;2;; if? of time at a constant temperature of 21 C. gc ngt oggsm 8g; 0%;7.4 4.3 After various periods of storage, samples were re- 8 H M 55moved and placed in pots in which sugar beet seedlings OH H weretransplanted. The pots were watered from below a and held'at 21 C. in agreenhouse. The phytotoxicity H was determined 1 week after thetransplanting. The following table gives the percentage of the plantsdestroyed. 02m NH\ 1 7.4 2.4 0

H K) NC TABLE D estructlon oi the 03H?! "NH L3 Plants inpercent H afterstorage NC (Weeks) 0.11.4 H CE; 7.7 5.1 Cmpwnds 0 1 2 3 4Cll-NHCzHd-NH-(XCHQzCN 95 a0 5 TABLE 4 Cl/-NHCH /NHC(CH )2CN 5 [X SCH RH} C 'NHO3HI'i/ "NH O(CH3)2CN 95 70 70 CHgSl-NHCgHd-NH 95 5 LeafPre-emer treatgence soil H R2 R3 R4 ment treatment NC 02H CH CH3 7.7 4.102H: CH3 02115 7.4 2.6. C1/-NHC2H5/NHC3H7-i (comparison) 95 95 95 95 9521 Example 27 The herbicidal activity of the following compounds wastested:

22 (1) 2-ethylamino-4-( l-cyanoethyl) -amino-6-methoxys-triazine (2)2-ethylamino-4-(1-cyanoethyl)-amino-6-methylmercapto-s-triazine 5 (32-methylamino-4- 1 -cyanopropyl -arnino-6-azido-s- (I) 2-ethylamino-4-(l-cyanoethyl) -amino-6-chloro-striazine After 18 days all plants weretotally destroyed.

Example 29 A mixed flora of corn, Wheat, barley, cotton, Digitariasanguinalis (crab grass), Plantago lanceolata (plantain), Cichoriumendivia (chicory), Echinochloa crus-ga'lli (barnyard grass), Amaranthusretroflexus (pigweed), cabbage and sugar beets was treated prior toemergence mercial product. In each instance the quantity of herbicide(kg/hectare) which was required for destruction of 10, 50 and 90% of theplants.

Substance (VI), 2 ethylamino-4-isopropylamin0-6- loro-triazine wasselected as the comparison substance.

All compounds correspond to the formula Cl NHCzH c1 NHCgH with varioustriazines and compared with a known com- Substance N0.

triazine chloro-s-triazine triazine (prior art) triazine (prior art) Thetests were as follows: (a) Post-emergence soil treatment.Various seeds15 were raked into soil in a greenhouse maintainedv at 21 C. Aftersprouting, a dispersion obtained by pouring a solution of the herbicidein equal quantities of Water if and to what extent the plant growth hadbeen reduced. (b) Leaf treatment.The procedure described under (a) wasfollowed except that the herbicide was applied The results of the testsare given in the following tables. The growth was evaluated according toa scale 25 ranging from 0 to 9 in which 0 signifies normal growth Theactive substance concentration in each instance TABLE.(a) POST EMERGENCESOIL TREATMENT Rye- Sugar Corn. Oats grass Peas Linseed Mustard beet (b)LEAF TREATMENT (II) 2-isopropylamino-4-( 1-cyanoethyl)-amino-6- (III)2-ethylamino-4-cyanomethylamino-6-chloro- (IV)2-ethylamino-4-(Z-cyanoethyl)-amino-6-chloro-s- (V)2,4,-bis-ethylamino-6-chlor0-s-triazine (prior art) was applied to thesoil. After 2 weeks it was determined to the plant leaves rather than tothe soil.

and 9 total destruction of the plant.

was 1 kg./hectare.

Substance tested l CaHr-l V7.......... OCHa NHCQH NHCHCN The results ofthe tests are given in the following table.

TABLE Dig. Plant. Cab- Sugar sang. lane. Cich. Echin. Amar. bage beetCorn Wheat Barley Cotton Example 28 A young mixed floro of Loliumperenne, Digitari sanguinalis, Alopecurus pratensis, Agropyren repensand V. No.

Plan'tago lancelolata was sprayed once with a 0.5% emulsion of thefollowing substances:

The table indicates that, for example, compounds V4 and V haveconsiderably stronger selectivity in cereals such as wheat and barleythan the comparison substance V1. It can furthermore be noted thatcompounds V2 and V3 in comparison with V1 have a stronger action againstcrab grass and barnyard grass while maintaining their selectivity incorn.

Example 30 Z-ethylamino 4-(1 cyanoethyl) amino-6 chloros-triazine wastested as to its ability to decompose in soil using the method disclosedin Example 26 but using a concentration of active substancecorresponding to 0.01 kg./hectare. The half value time for such compoundwas 2.5 weeks. In comparison the half value time of 2- ethylamino4-isopropylamino 6-chloro s-triazine when tested under the sameconditions was 6 weeks.

I claim:

1. A cyanoalkylamino substituted triazine of the formula wherein X isselected from the group consisting of halogen, lower alkoxy, lower alkylmercapto,

R1 N3 and N/ R and R being hydrogen, lower alkyl, lower alkenyl,substituted lower alkyl or substituted lower alkenyl in which latter twogroups the substituents are OH, OR, -SR or CN, R being lower alkyl, andwherein one of R and R is alkyl or alkenyl having from 1 to 8 carbonatoms and the other is hydrogen, alkyl or alkenyl having from 1 to 8carbon atoms, and wherein R and R together with the adjoining carbonatom may form a 5 to 7 member cycloalkyl ring.

2. The cyanoalkylarnino substituted triazine of claim 1 in which both Rand R are alkyl or alkenyl having from 1 to 8- carbon atoms and whereinR and R together with the adjoining carbon atom may form a 5 to 7 membercycloalkyl ring.

3. The cyanoalkylamino substituted triazine of claim 1 in which one of Rand R is hydrogen and the other is lower alkyl, lower alkenyl,substituted lower alkyl or substituted lower alkenyl, the substituentsin the latter two groups being as defined in claim 1.

4. The cyanoalkylamino substituted triazine of claim 1 in which X ishalogen.

5. The cyanoalkylarnino substituted triazine of claim 1 in which X ischlorine.

6. The cyanoalkylamino substituted triazine of claim 1 in which X ischlorine, and in which one of R and R is hydrogen and the other is loweralkyl, lower alkenyl, substituted lower alkyl or substituted loweralkenyl, the substitutions in the latter two groups being as defined inclaim 10, and in which both R and R are alkyl or alkenyl having from 1to 8 carbon atoms and wherein R and R together with the adjoining carbonatom may form a 5 to 7 member cycloalkyl ring.

7. The compound according to claim 1, which is 2- chloro 4 methylamino 6(1 cyano-1-methyl-ethyl)- amino-triazine.

8. The compound according to claim 1, which is 2- chloro 4 ethylamino 6(1 cyano 1 methyl-ethyl)- amino triazine.

9. The compound according to claim 1, which is 2- chloro 4 ethylamino 6(1 cyano-l-methyl-propyl)- amino-triazine.

10. The compound according to claim 1, which is 2- methoxy 4 ethylamino6 (l cyano-l-methyl-ethyl)- amino-triazine.

11. The compound according to claim 1, which is 2- methylmercapto 4ethylamino 6 (l-cyano-l-methylethyl) amino-triazine.

References Cited UNITED STATES PATENTS 3,399,194 8/1968 Mangini et a1.260-2493 XR 3,326,913 6/1967 Schulz et al. 260249.6 3,415,827 12/ 1968Nikles et a1 260-2498 HENRY R. JILES, Primary Examiner J. M. FORD,Assistant Examiner US. Cl. X.R.

